Leuco ester printing compositions and solubilizers therefor



Patented Feb. 17, 1953 UNITED STATES TENT OFFICE tion of Delaware me awatts. Application August 23, 1950, Serial No. 1915718 6 Claims.

The present invention w relates to the solubilization of leuco esters of vat dyestuifs to the compounds used for solubilization purposes, and to the compositions of such solubilizers and the leuco esters of a vat dyestufi. I

It is conventional practice to employ vat dyes in the form of their leuco estersalts, rather than in the form of thesiniple leuco compounds.

This is attributable to the'fact'that the leuco ester salts are more soluble than the leuco compounds-per se, a fact which facilitates the application of the reduced vat'dyes to the fiber.

These leuco ester saltsare' generally utilized for the printing of textiles by dissolving the ester salts in water and a thickening agent, applying the resulting paste to the fabric, and fixing the insoluble vat dyestuff on the fabric by subsequent hydrolysis and oxidation, The oxidizing agents glenerally'employedare sodium and ammeiiium salts.

some or the" leuco estrsaitsfaiie readily soluble inwaterbut others are considerably less soluble and are easily salted-out by electrolytes, such as the salts used as the oxidizing agents in forming the printing pastes. t, A 7

It has been proposed to facilitate the solubilizationof such leuco ester salts by adding compounds operating to effect dispersion of the salts. A group of compounds'which have found extensiveuse inthis'relationship are described in United- StatesLetters Patent 2,431,708; and are betaines or sulfobetaines containing an aralkyl radical. A very efie'ctive compound in this category is, for instance, the sulfobetaine of dimethyl benzyl' phenyl ammonium psulionic" acid. v t

We' ha've now found that compound's which we evn moree e uve in: the siolubilization of 329 Sal f. vat .dy et ff, han those. r crib i'ji igt e bq ..llsits a es pa en ar m usd 1f t h sl e eme W ite o t p nwh c a he qx ou r sl nked th u h a alkyl r kqni lk grou t9 h n tr se tom of; a; radical of the pyridine or quinolineseries,

platedhereim may be typifies a the following" structural formula wherein n is a number rangingfrom zero to 4;

derivative of the formula (4) p Sulfophenoxyethoxyethyl pyridinium derivative of the formula (5) of suifopiizi derivative of "the formula sulfonic (6) o Sulfophenoxyethoxyethyl quinolinium derivative of the formula OCHzCHzOCH2CHz-jbf The above compounds are prepared by the reaction of a phenoxy alkyl halide or a phenoxy alkoxy alkyl halide with the desired nitrogenous base, and subsequently sulfonating the product if desired.

The above products may be used for the solubilization of widely divergent types of leuco ester salts of vat dyestuffs. We have thus found them to be applicable in the solubilization of esters derived from indigos, thioindigos, indanthrenes, pyranthrones and the like. In all cases the solubilizing effect is permanent in that the print pastes remain stable and unprecipitated for many days.

For some reason for which we have no theory to offer, the phenoxy group in the above compounds adds appreciably to the solubilizing power of this class of compounds. It might be added that the unsubstituted phenoxy moiety contributes most to the solubilizing effect. Thus we have prepared compounds of the type contemplated herein from 2,4-dichlorophenol, 4-chlorophenol and 4-octylphenol. In every case the solubilizing effect of such compounds was poor.

Greater leeway, however, is allowed in the selection of the heterocyclic nitrogenous radical. Thus, the good results obtained, when such radical is pyridine, are likewise obtained when the pyridine is replaced by a-picoline, fi-picoline, the commercial mixture of B,'y-picolines, and quinoline. In some cases additions of compounds such as p-dimethylaniline sulfcnic acid improve the strength of the prints obtained with our compositions. However, these printing assistants are not necessary to obtain clear, smooth Y prints of excellent penetration.

The printing compositions are made up with our solubilizers according to the usual practice, to wit, they contain the leuco ester, an agglutinant such as starch tragacanth, an oxidizing agent such as sodium chlorate, ammonium chlorate or the like, a catalyst such as ammonium vanadate, and an acid splitter such as gluconic acid, ammonium sulfocyanide and the like. In use the pastes are applied to the fabric which are dried and steamed to effect development of the dyes thereon. The quantity of the solubilizer employed may vary but will usually range from about 100 to 200% by weight of the leuco ester employed.

The following examples will serve to illustrate the invention, but it is to be understood that the invention is not restricted thereto.

EXAMPLE 1 Preparation of Q-oomomocmom-rf '4 methanol until all of the chloride ion had been washed out and then it was washed with absolute ethyl alcohol. (This removes an oily product from the reaction.) The crude product was then dried in a vacuum desiccator. Yield= g. or about 50.6%.

EXAMPLE 2 Preparation of A mixture of 56.1 grams of phenoxyethyl bromide (Org. Syn. Coll., vol. I, p. 436), 54.4 grams of sodium pyridine-B-sulfonate and 100 cc. of water was heated at 120 C. for 20 hours in an autoclave. On cooling the sulfobetaine salt precipitated. It was filtered and washed first with 100 cc. ice water and secondly with 200 cc. acetone. The yield amounted to 63% of shiny white crystals sparingly soluble in cold water.

EXAMPLE 3 Preparation of ocnzcmo among-Ii (a) Quaternization of pyridine with phenom ethomyethyl chloride A solution of 153.6 grams of phenoxyethoxyethyl chloride and 63.2 grams of pyridine were heated at C. for 48 hours. After removing excess pyridine under vacuum, the thick oil remaining was induced to crystallize by scratching and cooling 206 grams of a crystalline solid were obtained.

(b) Sulfonation Twenty-five grams of this compound are sulfonated by heating with 30.0 grams of H2804 at 80 C. for 12 hours. The soluble Zwitter ion was isolated by standard liming out and evaporation technique.

EXAMPLE 4 The procedure is the same as in Example 3, excepting that the pyridine is replaced by a-DlCO- line.

EXAMPLE 5 The procedure is the same as in Example 3, excepting that the pyridine is replaced by quinoline.

EXAMPLE 6 A mixture is made of 3.5 grams of the assistant of Example 1, 4.0 grams of a 55% strength leuco ester of the vat dye of Example 2 of United States Letters Patent 1,095,731, 4.0 grams urea, 18.5 cc. hot water, 60 grams starch tragacanth, 4.0 cc. of sodium chlorate 1:3, 2.0 cc. ammonium vanadate 1:100, 2.0 cc. of ammonia 28%, 2.0 cc. gluconic acid 50%. A clear yellow solution is obtained which is stable on standing. This composition is printed on cotton and after drying is steamed 5 minutes. Bright full-bodied prints are obtained.

EXAMPLE '7 A mix of 3.5 grams of assistant mentioned in Example 2, 4.0 grams of a 55% leuco ester of bis- 2,1-naphthathiophen indigo, 4.0 grams of urea,

17.5 cc. water, 600 grams of'starch tragacanth, 4.9.: a fsQQ 1 m. hlo ate 3 mm ni vanadate 1:100, 4.0 cc. of ammoniumsulf ocye anide 1:1, 1.0 cc. of ammonia 28% is made. Part of the leuco ester is .precipitatedin very finely dividediorm. After dryingand steaming, rich brown shades are obtained which possess excel lentjpenetration in the cotton fiber.

EXANEPLE s 4.0 grams assistant of Example 3, 4.0 grams of the leuco ester of 4,4-dichloro16,6-dimethyl thioindigo, 5.0 grams of sodium'benzyl sulfinilate, 13.0 cc. hot water, 6.0 grams starch tragacanth,5.0 00. ammonium sulfocyanide, 6.0-cc. ammonium chlorate 1 :3, 2 cc. ammonium vanadate 1:100, 1 cc. ammonia 28% A finely divided suspension of the leuco ester is obtained. After printingin the accepted manner exceeding-1y bright 'jand' full prints were obtained. l

EXAMPLE 9 A mix of 4.0 grams of a 54% leuco ester of the vat dye described in United States Letters Patent 995,936, 4.0 grams of assistant of Example 1, 4.0 grams urea, 20.0 cc. water, 60 grams starch tragacanth, 8 cc. sodium chromate 1:5 is made. A clear reddish brown solution is obtained of the leuco ester. The prints are dried and steamed in acid fumes of formic and acetic acid five minutes. Pure strong prints are obtained.

EXAMPLE 10 A mix of 4.0 grams of assistant of Example 2, 4.0 grams of 55% of the leuco ester of the vat dye of Example 9 of United States Letters Patent 1,803,757, 10 cc. of glyecine, water, 50.0 grams of starch tragacanth, 2.0 cc. of ammonium sulfocyanide 1:1, 3.0 cc. sodium chlorate 1:3, 2.5 cc. ammonium vanadate 1:100, cc. ammonia 28%. A clear brown solution is obtained which is stable to storage, Prints are developed by steaming minutes in a rapid ager. Smooth and deep shades result from this procedure.

EXAMPLE 1 1 3.7 grams of assistant of Example 2, 4.0 grams of 55% of the leuco ester of Example 7, 6.0 cc. of furfuryl alcohol, water, 3.0 grams of sodium benzyl sulfinilate, 5.0 grams of diethyl tartrate, 20.3 cc. water, 50 grams starch tragacanth, 4.0 grams sodium chlorate 1:3, 2.0 grams of ammonium vanadate 1:100, 2 cc. ammonia 28%. Clear bright prints with excellent penetration are obtained.

EXAMPLE 12 O-o CH2CH2O 011201120 cream-Ii EXAMPLE 13 94 parts of phenol is mixed with 1 part sodium ethylate and theimixture heated in aniron pressure vessel with 220 parts of ethylene oxide to -100 C. (as in U. S. Patent 2,213,477) To the product-was slowly added 250 grams of thionyl chloride. After the initial reaction ceased, the.

solution was refluxed for three hours and permitted to stand overnight at room temperature. Afterremoval of the excess thionyl chloride by distillation, the product was distilled in vacuo.

The product was condensed with sodium. pyridine-3-sulfonate as in Example-1 to yield:

Quantitative measurements have been run with our compounds, and a compound described in United States Letters Patent 2,431,708, to wit, the dimethyl-benzyl-phenyl-ammonium-p-sulfonic acid thereof, and while using as the leuco ester the product of Example 2 above. The results of these measurements establish that our products solubilize from 15 to 25% more of such leuco ester than the prior art product. In the quality of penetration our compounds are also materially superior to said prior art compounds.

The very obvious commercial advantage of increased solubility of our preparations lies in the fact that less of the solubilizing agent is needed, and hence a greater concentration of dye may be employed.

Various modifications of the invention will occur to persons skilled in the art, and hence we do not intend to be limited in the patent granted excepting as necessitated by the prior art and the present claims.

We claim:

1. Compounds of the following formula [Go-mmomon-omomif 2] 3. The compound of the formula so; I

o-omqnni soQ 4. A dyestufi composition for printing textile fibers comprising an ester salt of a. leuco vat dyestuff and a compound of the following formula in which n is a number ranging from zero to 4, Z represents the atoms necessary to complete a radical selected from the class consisting of pyridine, C-lower alkyl pyridine and quinoline, and the group S03" is positioned on a carbon 6. A dyestufi composition for printing textile fibers comprising an ester salt of a leuco vat dyestuff and the compound of the following formula DAVID I. RANDALL. NICHOLAS W. SOLONEN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,299,782 Allen et a1. Oct. 27, 1942 2,336,465 Buck Dec. 14, 1943 2,388,285 Ratti et a1. Nov. 6, 1945 2,431,708 Ratti et a1. Dec. 2, 1947 FOREIGN PATENTS Number Country Date 684,432 Germany Nov. 28, 1939 OTHER REFERENCES Fieser et 81., Organic Chemistry (D. 0. Heath 0 and 00., Boston, 1944), page 32. 

1. A COMPOUNDS OF THE FOLLOWING FORMULA
 4. A DYESTUFF COMPOSITION FOR PRINTING TEXTILE FIBERS COMPRISING AN ESTER SALT OF A LEUCO VAT DYESTUFF AND A COMPOUND OF THE FOLLOWING FORMULA 